Method of forming anhydrous solid phase alkali metal salts of glycolonitrile



Patented Mar. 7 1950 'METHOD OF FORMING AN HYDROUS Q SOLID "PHASE ALKALI"METAL' SAI'ETS F 'GLYGO- Frederick"Ci-Bersworth, Verona, N. J.

No Drawing. Application September20,"194'6, -Serial No. 698,392

.16 Claims. 1

.This invention relates to chemistry iand'more particularly to organic'chemistryand"haszioriits object the provision cfraimethod of i forming:an-

hydrous nitrile compounds conforming to "the formula MO-CH2rCN whereinstands for ran alkali metal.

Another object is" to provide" a valuablewintermediate alkali metal'nitrile productuin the solid anhydrous phase for use in organicsynthesis reactions.

Other objects willbe apparent as the invention is' more fullyhereinafter disclosed.

I have discovered that when equal molar weights of an alkali metalcyanide, such :as sodium cyanide, and anhydrous formaldehyde, such asnaraformaldehyde -(CH2O) I 'or "trioxane (C3H6O3) are suspended in a nonreactiveiinert solvent such as petroleumether containing a relativelysmall amount or percentage of water functioning to produce a progressivelimited solutioning of the cyanide and formaldehyde for chemicalreaction, and the suspension is heated under a reflux condenser for anextended time to a refluxing temperature substant ally below thedecomposition temperature of the anhydrous formaldehydeand.approximatingj60p.C,, the suspended cyanide and paraformaldehydesaregraduallyidissolved in the water andarex reacted togethertto form analkali metal nitrile compound conforming to the formula MO-CI-Iw-CNwherein M stands for the alkali metal constituent of the cyanide,

- ride-formaldehyde water solution presentnand i soluble in thepetroleum ether .solvent present and i e i itated or crystall zed out ofsaid so- 'lutions in the form of anhydrousneedledikecrys- 'lihich ntrile is of l mited solubility inL-th-e'cyaout hydrolysis and suchsolvent solutions may be 'Ihe nitrile is highly reactive lwith alarge-number of organic compounds having active or dis placeablehydrogen atoms: to form'a lar-ge number of substitution compounds.

"These chemical =properties of the nitrilemake 'the nitrile a valuable fintermediate compound -in "organic synthesis reactions' as onle skilled-in 'the art will recognize. Heretoforeinthe-artftheexistence of such a'nitri-le compound-has been suspected but the compound, per se, hasnev-er as yet,

beenisolated and "all processes heretofore proposed whereinthis-compound is utilized-as a reactant are predicated upon itstheoretical and "transitory existence in'jaqueous solutions.

As aspecific embodiment"of-theipractice"ofthe present invention; but'notas a limitationoffthe "same; I' suspend-one molar weight of sodiumicyanide andone'molar weight of. anhydrousformaldehyde (paraformaldehydeor trioxane) in about cubic centimeters ofpetroleum ether and; addIthereto about. .01-I05. cubic centimeter of water, preferablyad'dedinftheform of'981% ethyl alcohol. This .mixture' is placediinl a glass i.container closedito the "atmosphere a reflux con- .denseriand the,mixture is heated Withponstaiit stirring, to the refluxing temperature.of the ,pe-

,,troleum ether (40-60". C.)

The'heating and stirring is continued iforaa ,period of timesapproximating .1-w-2 hours, i or until the reaction between thecyanideiandtthelformreactionsproduct.

Various: experimentshave indicated that the re- ..actionproceedsiquantitatively to completion and the recoveries obtainableclosely approximate 100% of the theoretical. such losses as may occurbeing primarily due to the mechanical losses on filtering and to suchlosses as may be incident to solution in the amount of water present. Toavoid greater losses due to hydrolysis the heating should be terminatedas soon as complete reaction is noted. Various tests using determinedamounts of materials will indicate the approximate maximum time intervalof heating for maximum recoveries.

In the above reaction, the amount of water employed should be held tothe minimum amount required to promote the reaction by progressivesolution otlthe sodium cyanide and paraformalde- V hyde for liquid phasecontact reaction therebetween at the temperature of heating, within an(CH O)a+ 3NaCN H In the practice of this invention it is advantageous toexclude air and atmospheric moisture from the reflux condenser byintroducing a pressure of an inert gas such as nitrogen within thecontainer, the pressure being sufficient to exclude the atmosphere fromthe container.

From the above disclosure of the present invention it is believed anyone skilled in the art may duplicate the invention and all suchmodifications and departuresfrom the specific embodiment given arecontemplated as may fall within the scope of the following claims.

What I claim is:

1. The method of producing an anhydrous nitrile which comprisessuspending an alkali metal cyanide and anhydrous formaldehyde inpetroleum ether, adding a small amountof water to the suspensionsufficient to dissolve only a small proportion of the cyanide andformaldehyde present in the suspension and heating the suspension withagitation under a reflux condenser to temperatures above 40 C. but notover about 70 C.

2. The method of producing an anhydrous nitrile which comprisessuspending an alkali metal cyanide and anhydrous formaldehyde inpetroleum ether, adding a small amount of water to the suspensionsufficient to dissolve only a small proportion of the cyanide andformaldehyde present in the suspension and heating the suspension withagitation under a reflux condenser to temperatures above 40 C. but notover about 65 0., and under a positive pressure of nitrogen excludingatmospheric gases from the reflux condenser.

8. The method of producing a nitrile compound conforming to the formulaNaO.CHz.CN which comprises suspending equal molar weights of an alkalimetal cyanide and paraformaldehyde in petroleum ether, adding a smallamount of water to the suspension suflicient to dissolve only a smallproportion of the cyanide and formaldehyde present in the suspension,and heating the suspension to the refluxing temperature of the petroleumether for an extended time interval suflicient to obtain substantiallycomplete progressive solution of the cyanide and aldehyde in the waterand reaction therebetween with precipitation of the anhydrous nitrileproduct formed.

4. The method of producing an anhydrous nitrile conforming to theformula NaO.CHz.CN which comprises suspending equal molar weights ofsodium cyanide and formaldehyde each in its anhydrous state in anon-aqueous solvent having a refluxing temperature substantially belowthe decomposition temperature of the anhydrous formaldehyde, adding asmall amount of water thereto sufficient to dissolve only a smallproportion of the cyanide and formaldehyde present in the suspension,and heating the suspension with agitation to the refluxing temperatureof the solvent for an extended time interval sufficient to obtainsubstantially complete progressive solution of the cyanide andformaldehyde in the water present and reaction of the same to thenitrile compound and its precipitation in anhydrous form in suspensionin the said solvent, cooling the suspension to atmospheric temperaturesand separating the precipitated nitrile from the liquid phase productsassociated therewith.

5. The method of claim 4 wherein said solvent consists of petroleumether having a refluxing temperature Within the range 40-60 C. andwherein the temperature of heating approximates C.

6. The method of claim 4, wherein a positive pressure of an inert gas ismaintained within the reflux condenser to exclude atmospheric gases fromthe reaction.

FREDERICK C. BERSWORTH.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,984,415 Macallum Dec. 18, 19342,101,823 Dittmar Dec. 7, 1937 2,387,735 Bersworth Oct. 30, 1945 FOREIGNPATENTS Number Country Date 300,040 Great Britain Nov. 8, 1928 654,713Germany Jan. 4, 1938 OTHER REFERENCES Polstorfi et al., Ber. Deut. Chem,vol. 45, pp. 1905-1912 (1912).

1. THE METHOD OF PRODUCING AN ANHYDROUS NITRILE WHICH COMPRISESSUSPENDING AN ALKALI METAL CYANIDE AND ANHYDROUS FORMALDEHYDE INPETROLEUM ETHER, ADDING A SMALL AMOUNT OF WATER TO THE SUSPENSIONSUFFICIENT TO DISSOLVE ONLY A SMALL PROPORTION OF THE CYANIDE ANDFORMALDEHYDE PRESENT IN THE SUSPENSION AND HEATING THE SUSPENSION WITHAGITATION UNDER A REFLUX CONDENSER TO TEMPERATURES ABOVE 40*C. BUT NOTOVER ABOUT 70*C.